Hydrogenolysis of butane

Reactivity studies of organic ligands with mixed-metal clusters have been utilized in an attempt to shed light on the fundamental steps that occur in heterogeneous catalysis (Table VIII), although the correspondence between cluster chemistry and surface-adsorbate interactions is often poor. While some of these studies have been mentioned in Section ll.D., it is useful to revisit them in the context of the catalytic process for which they are models. Shapley and co-workers have examined the solution chemistry of tungsten-iridium clusters in an effort to understand hydrogenolysis of butane. The reaction of excess diphenylacetylene with... 

Table 1. Hydrogenolysis of butane by supported Rh and RhPt catalysts.

Hydrogenolysis of butane was used to study the catalysis of the RhPt particles in mesoporous silica. This is a test reaction of reforming of alkanes in oil refinery, and methane, ethane, and propane are formed by the cleavage of terminal or central C-C bond (Scheme 1). 

This hypothesis of secondary cleavage is confirmed in the hydrogenolysis of butane (Figure 3.22). At low conversion, one observes the formation of ethane. 

Hydrogenolysis of butane was performed using Pt and PtRh nanowires and particles/FSM-16 [23, 32] Table 15.6 summarizes the results. In this reaction, methane, ethane and propane were formed from hydrogenolysis of butane, and isobutane from isomerization (15.1) ... 

Figure 13.11. Dependence of rate of hydrogenolysis of -butane on hydrogen pressure at various temperatures on Pt/AbOs (EUROPT-3). 5...

Engstrom J R, Goodman D Wand Weinberg W H 1986 Hydrogenolysis of n-butane over the (111) and (110)-(1 2) surfaces of iridium a direct correlation between catalytic selectivity and surface structure J. Am. Chem. Soc. 108 4653... 

Engstrom J R, Goodman D W and Weinberg W H 1988 Hydrogenolysis of ethane, propane, n-butane and neopentane... 

The reaction scheme is rather complex also in the case of the oxidation of o-xylene (41a, 87a), of the oxidative dehydrogenation of n-butenes over bismuth-molybdenum catalyst (87b), or of ethylbenzene on aluminum oxide catalysts (87c), in the hydrogenolysis of glucose (87d) over Ni-kieselguhr or of n-butane on a nickel on silica catalyst (87e), and in the hydrogenation of succinimide in isopropyl alcohol on Ni-Al2Oa catalyst (87f) or of acetophenone on Rh-Al203 catalyst (87g). Decomposition of n-and sec-butyl acetates on synthetic zeolites accompanied by the isomerization of the formed butenes has also been the subject of a kinetic study (87h). 

The case of butane is noteworthy since the selectivity at low conversions indicates that there is no selectivity in the overall hydrogenolysis step between n- and sec-butyl zirconium surface intermediates, while earUer studies had shown that the -alkyl zirconium complexes were more stable than sec-alkyl derivatives (Table 3 and Scheme 23) [94]. 

Other types of non-micro-channel, non-micro-flow micro reactors were used for catalyst development and testing [51, 52]. A computer-based micro-reactor system was described for investigating heterogeneously catalyzed gas-phase reactions [52]. The micro reactor is a Pyrex glass tube of 8 mm inner diameter and can be operated up to 500 °C and 1 bar. The reactor inner volume is 5-10 ml, the loop cycle is 0.9 ml, and the pump volume adds a further 9 ml. The reactor was used for isomerization of neopentane and n-pentane and the hydrogenolysis of isobutane, n-butane, propane, ethane, and methane at Pt with a catalyst. 

These surface hydrides are active catalysts for the hydrogenolysis of alkanes at moderate temperatures. Zirconium hydride can catalyze the hydrogenolysis of neopentane, isobutane, butane, and propane at 323 K but cannot catalyze the hydrogenolysis of ethane.259... 

Having set out the properties of tantalum and zirconium hydride toward C-H bond activation of alkanes we now describe the catalytic hydrogenolysis of C-C bonds. It was previously shown in the laboratory that supported-hydrides of group 4 metals, and particularly of zirconium, catalyze the hydrogenolysis of alkanes [21] and even polyethylene [5] into an ultimate composition of methane and ethane. However, to our initial surprise, these zirconium hydrides did not cleave ethane. (=SiO)2Ta-H also catalyzes the hydrogenolysis of acyclic alkanes such as propane, butane, isobutane and neopentane. But, unlike the group 4 metals, it can also cleave ethane [10], Figure 3.7 illustrates this difference of behavior between (=SiO)2Ta(H) and [(=SiO)(4.j,)Zr(H) ], x= or 2). With Ta, propane is completely transformed into methane by successive reactions, while with Zr only equimolar amounts of methane and ethane are obtained. 

Figure 3.22 Butane hydrogenolysis products (a) selectivity (b). Conditions 160°C, 40Torr of butane (40 equiv./M),...

Figure 3.36 Particle size distribution of Pt/silica (a) (red) and Pt/Sn on silica (b) (blue) (c) evolution of n-butane during the hydrogenolysis of Sn("Bu)4 as a function of time of preparation and, after 40h, as a function of temperature (from 50 up to 400°C).

Hydrocarbons higher than C3 can also undergo isomerization on Pt, running in parallel to hydrogenolysis. With butane or isobutane the selectivity for isomerization is rather low, also on Pt, but the higher hydrocarbons show more of isomerization reactions. With higher hydrocarbons some other metals (Ir, Pd) also show some isomerization selectivity. 

The catalytic hydrogenation of 7,7-dihalonorcaranes proceeds with opening of the three-membered ring and leads ro methylcyclohexane, whereas the reduction with sodium in alcohols affords norcarane [2], Hydrogenolysis of l,l-difluoro-2-methyl-3-phenylcyclopropane in the presence of a Ni—Re or Pd catalyst at atmospheric pressure provides a mixture of 1 -phenyl-butane, l-phenyl-2-fluorobutane, and l-phenyl-2,2-difluorobutane, respectively [25],... 

Catalytic hydrogenolysis of light alkanes (propane, butanes, pentanes) with the exception of ethane has been accomplished under very mild conditions over silica-supported hydride complexes.502 The hydrogenolysis proceeds over (=SiO)3 ZrH,503 (=SiO)3HfH,504 and (=SiO)3TiH505 by stepwise cleavage of carbon-carbon bonds by P-alkyl elimination from surface metal-alkyl intermediates. 

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